CN103774072A - Flux compositions for steel galvanization - Google Patents
Flux compositions for steel galvanization Download PDFInfo
- Publication number
- CN103774072A CN103774072A CN201310507727.4A CN201310507727A CN103774072A CN 103774072 A CN103774072 A CN 103774072A CN 201310507727 A CN201310507727 A CN 201310507727A CN 103774072 A CN103774072 A CN 103774072A
- Authority
- CN
- China
- Prior art keywords
- zinc
- weight
- chloride
- plated
- flux composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 126
- 230000004907 flux Effects 0.000 title claims abstract description 114
- 239000010959 steel Substances 0.000 title claims abstract description 93
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 74
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011701 zinc Substances 0.000 claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 33
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 32
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 19
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 18
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 16
- 239000011592 zinc chloride Substances 0.000 claims abstract description 16
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims abstract description 8
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 7
- 239000011253 protective coating Substances 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims description 35
- 230000008018 melting Effects 0.000 claims description 34
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 32
- 239000004411 aluminium Substances 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 238000007654 immersion Methods 0.000 claims description 9
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 150000008045 alkali metal halides Chemical class 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000005246 galvanizing Methods 0.000 abstract description 24
- 229910045601 alloy Inorganic materials 0.000 abstract description 18
- 239000000956 alloy Substances 0.000 abstract description 18
- 239000010410 layer Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 30
- 238000005554 pickling Methods 0.000 description 19
- -1 zinc-aluminium-magnesium Chemical compound 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 229910001297 Zn alloy Inorganic materials 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 229910007570 Zn-Al Inorganic materials 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 7
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 235000019197 fats Nutrition 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- 229910052728 basic metal Inorganic materials 0.000 description 6
- 150000003818 basic metals Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000010561 standard procedure Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000002075 main ingredient Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910001208 Crucible steel Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 208000034189 Sclerosis Diseases 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 238000003287 bathing Methods 0.000 description 3
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- 239000010974 bronze Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000635 Spelter Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 238000004880 explosion Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- 229910052738 indium Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000002577 pseudohalo group Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/30—Fluxes or coverings on molten baths
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention relates to flux compositions for steel galvanization. This invention relates to a flux composition for treating a metal surface prior to batch hot galvanizing in molten zinc-based alloys. The composition comprises (a) more than 40 and less than 70 wt.% zinc chloride, (b) 10 to 30 wt.% ammonium chloride, (c) more than 6 and less than 30 wt.% of a set of at least two alkali or alkaline earth metal halides, (d) from 0.1 to 2 wt.% lead chloride, and (e) from 2 to 15 wt.% tin chloride, provided that the combined amounts of lead chloride and tin chloride represent at least 2.5 wt.% of said composition. The invention further relates to a fluxing bath comprising this flux composition dissolved in water for use in galvanizing processes, by batch or continuously, of metal articles such as iron or steel long products and flat products, thus affording a protective coating layer with a thickness ranging from 5 to 30 [mu]m.
Description
Technical field
The present invention relates to zinc-plated field, relate more specifically to galvanizing or galvanizing coating.Particularly, the present invention relates to the zinc-plated of iron material, such as but not limited to iron, cast iron, steel and cast steel.More specifically, the present invention relates to a series of flux composition, its surface for processing iron material (as iron and steel) before the molten bath immersing based on zinc.The present invention also relates to (1) galvanized method, in at least one procedure of processing, use particularly the galvanizing of flux composition, and (2) zinc-plated product, comprise the zinc-plated iron product (for example, band steel and long product made from steel) by manufacturing by the method for fluxing agent compositions-treated product surface.
background of invention
As everyone knows; provide protection to prevent iron (as iron and the steel) goods that use out of doors; for example, as the importance of fence, metal wire, bolt, cast iron bend pipe and trolley part corrosion, and to apply iron material with zinc be the very effective and economic mode achieving this end.Conventionally by immersing or making to need the goods of coating to implement spelter coating through the molten bath of metal.This operation is called as term " zinc-plated ", " pot galvanize " or " galvanizing " (HDG) so that itself and zinc electro-plating method are distinguished.In this method, product surface form the cured layer of zinc and the spelter coating that forms thus by the mutual alloy of iron/zinc that forms in galvanizing process and the surperficial mortise of goods.Oxide compound or other foreign matters (" dirt (soil) ") on steel work surface can disturb the chemical property of galvanized method and stop even, the continuous coating without hole of formation.Therefore the combination that, has adopted various technology and technology in industry is to reduce as much as possible, to eliminate or at least to adapt to oxide compound and dirt.
Can realize by the alloy of zinc and aluminium and/or magnesium the character improvement of galvanizing production.Add the aluminium of 5 % by weight to produce compared with the alloy of low melting point (eutectoid point is at 381 ℃), it shows the discharging properties (drainage property) of improvement with respect to pure zinc.In addition, the coating that the galvanizing coating producing with this Zn-Al alloy forms than substantially pure zinc has plasticity and the better coating property of stronger erosion resistance, improvement.But zinc-aluminium is zinc-plated is responsive especially for surface clearness, to such an extent as to runs into all difficulties when at zinc-plated middle use Zn-Al alloy, as inadequate steel surface wettability.
In industry, adopt a lot of technology and combination thereof to reduce as much as possible, to eliminate or at least to adapt to oxide compound and dirt.Substantially in all these methods, first by making to want the surface of coating to contact (alkali cleaning) removal organic dirt (as oil, grease, antirust compound) with alkaline water lotion.This can be by other technology as scrubbed, supersound process and/or electricity wash realization.Then water rinses, and makes surface contact to remove iron particle and oxide compound (pickling) with acidic aqueous washing lotion, and final water rinses again.For most of galvanizing techniques, the method for all these washing-pickling-flushing is routine and industrial or accurately or roughly implements.
The another kind of pretreatment process for high-strength steel, high carbon steel, cast iron and cast steel is the mechanical cleaning method that is called sandblast (blasting).In this method, by the little particle of the jet surface to this steel or iron and grit, from this surface removal iron rust or dirt.According to the shape of parts to be processed, size and thickness, use different sandblast machines as the upset sandblast machine for bolt, for passage sandblast machine of trolley part etc.
On clean metal (as iron or steel) parts, use two kinds of main galvanizing techniques: (1) melting method, and (2) Annealing furnace method.
First galvanizing technique, i.e. melting method, itself can be divided into two classifications, dry melting method and wet melting method.
Dry melting method, it can be combined with one or more in above-mentioned cleaning, pickling or sandblast scheme, forms salt deposit by metal parts being immersed to the water bath (being called " pre--flux (pre-flux) ") that contains chloride salt on ferrous metal surface.Afterwards, dry this layer before zinc-plated operation, thereby protection steel surface is avoided being again oxidized, it immerses fused zinc bathes.Like this pre--flux contains watersoluble chlorinated zinc and optional ammonium chloride conventionally, have been found that its existence improved the wetting properties of product surface fused zinc and therefore promote to form evenly, continuously, without the coating in hole.
The wet concept melting is to replace zinc-plated bath with top flux (top flux), and described top flux also generally includes zinc chloride and frequent ammonium chloride, but in this case, these salt are on top melting and that swim in zinc-plated bath.To pre--flux is similar, the object of top flux is to provide zinc chloride and preferred ammonium chloride to improve wetting properties in zinc-plated to system.In this case, when steel part is through top flux layer and while immersing zinc-plated still, all remaining oxide on surface and dirts after cleaning-pickling-flushing are all removed.Wet melting has some shortcomings, as compares the dry much more zinc of consumption that melts, and produces much more flue gas etc.Therefore, today, their technique was changed into dry melting method in most zinc-plated factory.
It is below the general introduction of Annealing furnace method.In use zinc or zinc-aluminium or the continuation method of zinc-aluminium-magnesium alloy as zinc-plated medium, under reducing atmosphere, (as the mixture of nitrogen and hydrogen) anneals.This has not only eliminated the surperficial oxidation again of cleaning before, pickling and flushing, has in fact also removed any residual oxide on surface and the dirt that may still exist simultaneously.Most steel ring today (steel coil) is zinc-plated according to this method.Very important requirement is that steel ring is not having under any contact with air, leaves Annealing furnace by directly entering continuously fused zinc.But this requirement makes it for the parts that are shaped, or for steel wire, use this technology extremely difficult, because steel wire breakage is too frequent and Annealing furnace method does not allow to be interrupted.
Another technology for the production of zinc-aluminium galvanizing coating comprises and (if 0.5-0.7 μ zinc m) is to steel work electricity-coating (being hereinafter called " pre--apply "), dryly in the process furnace of air atmosphere then immersing in zinc-plated still through pre--goods of applying with thin layer.This in the hot-dip coating of the steel pipe of continuous lines, be widely used and in production at steel bar usage degree lower.Although this does not require under reducing atmosphere and process, its shortcoming is to require other metal-coating step.
Implement zinc-plated with batchwise operation or operate continuously.Operate continuously is implemented conventionally on the goods that can carry out this type operations, as metal wire, sheet material, bar, pipe etc.In operate continuously, between continuous treatment step, the transfer of goods is very fast and automatically completes continuously, and operator are on the scene to deal with problems with supervisory work with when problem occurs.The production capacity of operate continuously is very high.Relate to make use pre--flux then in process furnace in dry continuous zinc coating line, from pre--flux tank, shift out goods to immersing time of consuming zinc-plated bath conventionally in about 10-60 second, rather than 10-60 minute in batch processes.
Batchwise operation is quite difficult.In the lower and zinc-plated part of production capacity, in shape more under complicated situation, batchwise operation is preferred.For example, the steel part of various manufactures, structural steel shape and steel pipe are preferably zinc-plated in batchwise operation.In batchwise operation, need the parts of processing by be manually transferred in each continuous treatment step in batches, be not almost with or without and relate to automatic operation.This is illustrated in time that each several part in concrete treatment step stops will be much larger than the time in operate continuously, and more significantly, there is larger variation the time in time and operate continuously between continuous treatment step.For example, in the batch processes of common galvanized steel pipe, a collection of nearly 100 steel pipes are bathed in (pre-flux bath) and are immersed and transfer to platform upper feeding by each one of the mode of manual operation crane afterwards at pre--flux together, enter in zinc-plated bath.
Due to the step between batchwise operation and operate continuously and scale difference, in a generic operation, useful especially technology is not inevitable useful in another kind of technology.For example, in business or technical scale, the use of reductibility process furnace only limits to operate continuously.Meanwhile, it is valuable that the high throughput rate relating in continuation method makes to preheat for providing additional heat to zinc-plated bath.In batch processes, time of lag is longer and throughput rate is lower, and therefore the heat energy consumption speed of zinc-plated bath is much lower.
There is the demand of the good plasticity of ferrous metal goods and the non-corrosibility combination of enhancing.But, before the alloy coat based on zinc that contains a large amount of aluminium (or optional, magnesium) can be introduced into common zinc-plated industry, must overcome difficulty below:
-contain high aluminium content zinc alloy almost can not with standard zinc-aluminium muriate flux produce.Previously propose to contain metal Cu or the sedimental flux of Bi, there is no magnetism but copper or bismuth infiltrate the possibility of zinc bath.Therefore, need better flux.
The alloy of-high aluminium content is tending towards forming the explosion of the mutual alloy of zinc-iron, and this is disadvantageous in zinc-plated last stages.This phenomenon causes very thick, uncontrolled and coarse coating.The control of explosion is completely essential.
-in the Zn-Al alloy that contains high aluminium content, report before wetting properties problem, may be owing to comparing the surface tension that pure zinc is larger.Therefore because the bad moistening of steel is easy to form bare spot, and therefore need to reduce the surface tension of melt.
-in the Zn-Al alloy that contains high aluminium content, report the poorly controlled of coat-thickness, this may depend on as the parameter of quality of temperature, flux composition, immersion time, steel etc.
WO02/42512 has described the flux for galvanizing, the zinc chloride that it contains 60-80 % by weight; The ammonium chloride of 7-20 % by weight; At least one basic metal or the alkaline earth salt of 2-20 % by weight; 0.1-5 % by weight be selected from NiCl
2, CoCl
2and MnCl
2in at least one; And 0.1-1.5 % by weight be selected from PbCl
2, SnCl
2, SbCl
3and BiCl
3in at least one.The NaCl that preferably this flux contains 6 % by weight and the KCl of 2 % by weight.Embodiment 1-3 discloses the flux composition that comprises 0.7-1 % by weight lead chloride.
WO2007/146161 has described and has carried out zinc-plated method with fused zinc-alloy, said method comprising the steps of: the iron material that (1) applies needs is immersed in the independently flux of container and bathes in (flux bath), thereby manufacture the iron material that flux applies, and (2) iron material of afterwards flux being applied Zn-Al alloy of being immersed in the melting of separation vessel bathe in to apply Zn-Al alloy layer, the aluminium that wherein Zn-Al alloy of melting comprises 10-40 % by weight, the silicon of at least 0.2 % by weight, all the other are for zinc and optionally comprise that one or more are selected from the extra elements of magnesium and rare earth element.In step (1), flux is bathed the zinc chloride that can comprise 10-40 % by weight, the ammonium chloride of 1-15 % by weight, and alkaline earth metal chloride, tensio-active agent and the acidic components of 1-15 % by weight, the final pH that makes flux is 1.5 or lower.In another embodiment of step (1), flux is bathed and can be defined as WO02/42512.
JP2001/049414 has described by containing 61-80 % by weight zinc chloride, 5-20 % by weight ammonium chloride, in the muriatic flux of one or more Sn, Pb, In, Tl, Sb or the Bi of one or more basic metal of 5-15 % by weight or muriate, fluorochemical or the silicofluoride of alkaline-earth metal and 0.01-5 % by weight, carry out hot dipping, the steel plate of the alloy-coated based on Zn-Mg-Al of production hot dipping, it has outstanding erosion resistance.More specifically, the table 1 of JP2001/049414 has been described the flux composition of the various KCl/NaCl of containing weight ratios at 0.38-0.60, when it is for containing 0.05-7 % by weight Mg, 0.01-20 % by weight Al, all the other are in the steel plate in the bath of molten alloy of zinc time, good plating ability is provided, there is no pinprick, has there is no scum silica frost and good planeness.On the contrary, the table 1 of JP2001/049414 has described that to contain KCl/NaCl weight ratio be 1.0 flux composition, when it is for containing 1 % by weight Mg, 5 % by weight Al, all the other are in the steel plate in the bath of molten alloy of zinc time, and poor plating ability, pinprick defect, some scum silica frost and poor planeness is provided.
Therefore, the general enlightenment of prior art is lower than 1.0 in the weight ratio that melts preferred KCl/NaCl in composition.But prior art does not still solve listed most of technical problems herein.The final demand that still has in the art the melting composition of improvement and the galvanized method of use said composition.
Summary of the invention
The object of this invention is to provide flux composition makes it possible to by with pure zinc or zinc alloy, specifically the Zn-Al alloy of various compositions and zinc-aluminium-magnesium alloy carry out galvanizing, at metal products, on the ferrous products of arbitrary shape or steel work, produce specifically continuously, more evenly, the more smoothly and not coating containing hole.Surprisingly find that this can be by provide lead chloride and the tin chloride realization of specified quantitative simultaneously in flux composition.Therefore solved the above-mentioned most problems of mentioning by flux composition as defined in claim 1 and galvanized method as defined in claim 7.In dependent claims 2-6 and 8-10, define embodiment.
detailed Description Of The Invention
Principal character of the present invention is understanding in the time that selection comprises separately the lead chloride of specified quantitative and the flux composition of tin chloride (prerequisite is that their combined amount exceedes previously from the above-mentioned specific threshold of known in the literature) simultaneously, realize at metal, specifically the huge improvement in iron and steel zinc-plated.This principal character is relevant to the specified quantitative of other components of flux composition, as claim 1 defines.
definition
Term " galvanizing " refers in operate continuously or batchwise operation; pass through metal products; such as but not limited to iron or steel work, immerse in the flux bath of pure zinc or zinc alloy, maintain the corrosion treatment of time enough with the product surface formation protective layer described.Term " pure zinc " refers to some additives that may contain trace, for example zinc-plated bath of the zinc of antimony, bismuth, nickel or cobalt.This is contrary with " zinc alloy ", and one or more other metals that it contains obvious amount, as aluminium or magnesium.
Hereinafter, the different per-cent relevant from the part by weight (% by weight) of each component is the gross weight (100%) with respect to flux composition or the bath based on zinc.This represents to meet 100 % by weight for sum, and not every maximum or minimum percent can exist simultaneously.
Flux composition of the present invention comprises, as a necessary feature, and 0.1-2 % by weight lead chloride and 2-15 % by weight tin chloride, prerequisite is that lead chloride and tin chloride account at least 2.5 % by weight in described composition.The flux composition of each embodiment of the present invention defines and is described in further detail as claim 2-11.
In one embodiment, in flux composition, the ratio of lead chloride is at least 0.4 % by weight or at least 0.7 % by weight.In another embodiment, in flux composition, the ratio of lead chloride is 1.5 % by weight or at the most 1.2 % by weight at the most.In embodiment, in flux composition, the ratio of lead chloride is 0.8-1.1 % by weight.
In one embodiment, in flux composition, the ratio of tin chloride is at least 2 % by weight or at least 3.5 % by weight or at least 7 % by weight.In another embodiment, in flux composition, the ratio of tin chloride is 14 % by weight at the most.
In one embodiment, at least 4.5 % by weight that the combined amount of lead chloride and tin chloride is flux composition in flux composition or at the most 14 % by weight.In another embodiment, flux composition also can comprise the salt of other lead and/or tin, for example fluorochemical, or other chemical of the inevitable impurity existing in other lead chlorides in commercially available source and/or tin chloride.
In one aspect of the invention, in flux composition, specified quantitative separately of lead chloride and tin chloride and the muriatic combination of every other specified proportion make it possible to especially in batchwise operation or operate continuously, by zinc-plated, especially galvanizing, with fused zinc or the alloy based on zinc at metal products, especially on ferrous products and steel work, produce continuous, more evenly, more smoothly and not containing the coating in hole.
For example, in flux composition the amount separately of lead chloride and tin chloride with exceed 40 % by weight and the zinc chloride combination less than 70 % by weight.In one embodiment, in flux composition, the ratio of zinc chloride is at least 45 % by weight or at least 50 % by weight.In another embodiment, in flux composition, the ratio of zinc chloride is 65 % by weight or at the most 62 % by weight at the most.ZnCl in composition like this
2ratio, with the amount separately combination of lead chloride in flux composition and tin chloride under, can guarantee to need effectively to prevent in the well applied of zinc-plated metal products and dry before follow-up procedure of processing is as zinc-plated in itself oxidation of metal products.
In one aspect of the invention, the amount separately of lead chloride and tin chloride and the combination of the ammonium chloride of 10-30 % by weight in flux composition.In one embodiment, NH in flux composition
4the ratio of Cl is at least 13 % by weight or at least 17 % by weight.In another embodiment, in flux composition, the ratio of ammonium chloride is 26 % by weight or at the most 22 % by weight at the most.NH
4the best proportion of Cl can not have great many of experiments and not rely on metal as zinc-plated in needs and the parameter of the part by weight of metal chloride, use the experimental evidence as shown in the following examples by simple in flux composition, determined by those skilled in the art, to realize sufficient etch effect to remove the incomplete site of residual iron rust or pickling in hot dipping process, avoid forming stain, i.e. the uncoated region of metal products simultaneously.Under some environment, available one or more alkyl quaternary ammonium saltss substitute the smaller portions NH of (as being less than 1/3 weight)
4cl, wherein as described in EP0488423, at least one alkyl group has 8-18 carbon atom, for example chlorination alkyl-trimethyl ammonium (for example chlorination trimethylammonium lauryl ammonium) or chlorination dialkyl dimethyl ammonium.
In one aspect of the invention, in flux composition the amount separately of lead chloride and tin chloride also with one or more of suitable amount, preferably several, alkali metal halide or alkaline earth metal halide combination.This Pseudohalides is preferably or mainly muriate (available bromide, but due to not preferred fluorinated thing of security reason), and basic metal or alkaline-earth metal are to be preferentially selected from Na, K, Li, Cs, Mg, Ca, Sr and Ba (with reference to each metals with the order sequence of successively decreasing).Flux composition should preferably include the halid mixture of these alkali and alkaline earth metal ions, because such mixture is tending towards increasing molten mixture for the average chemical affinity of chlorine and provides synergy better or more accurately to control fusing point and the viscosity of melting salt, thereby better or more accurately controls wetting properties.In one embodiment, the halid mixture of basic metal or alkaline-earth metal is one group of at least two kinds of alkali metal chloride and the 10-30 % by weight that accounts for flux composition.In another embodiment, one group of at least two kinds of alkali metal chloride comprises sodium-chlor and the Repone K as main ingredient.In another embodiment, one group of at least two kinds of alkali metal chloride (as the NaCl as main ingredient and KCl) account at least 12 % by weight or at least 15 % by weight of flux composition.In another embodiment, one group of at least two kinds of alkali metal chloride (as comprising sodium-chlor and the Repone K as main ingredient) account for 25 % by weight at the most of flux composition or 21 % by weight at the most.In another embodiment, in flux composition, the ratio of at least two kinds of alkali metal chlorides (as the sodium-chlor as main ingredient and Repone K) is 20-25 % by weight.In each above-mentioned embodiment, NaBr, KBr, MgCl
2and/or CaCl
2can be used as accessory constituent exists.
In one aspect of the invention, in flux composition the amount separately of lead chloride and tin chloride also with the muriate combination of one or more other metals (as transition metal or rare earth metal) of suitable amount, as nickelous chloride, cobalt chloride, Manganous chloride tetrahydrate, Cerium II Chloride and Lanthanum trichloride.For example, some examples below prove that the existence of nickelous chloride of as many as 1 % by weight (even as many as 1.5 % by weight) is not disadvantageous for the performance of flux composition with regard to obtaining the quality of coating after galvanizing.
In order to realize best possible advantage, the ratio between these alkali metal halides and alkaline earth metal halide is very important.The mixture of alkali metal halide or alkaline earth metal halide can be the one group at least two kinds alkali metal chlorides that comprise sodium-chlor and Repone K, and KCl/NaCl weight ratio is 0.2-1.0.In one embodiment, the weight ratio of KCl/NaCl can be 0.25-0.6.In one embodiment, the weight ratio of KCl/NaCl can be 1.0-2.0.The mixture of also surprisingly finding alkali metal halide or alkaline earth metal halide is that the flux composition of one group of at least two kinds of alkali metal chloride comprising that the KCl/NaCl weight ratio of sodium-chlor and Repone K is 2.0-8.0 shows remarkable character.In one embodiment, the weight ratio of KCl/NaCl can be 3.5-5.0, or 3.0-6.0.
In other aspects of the present invention, the amount separately of lead chloride and tin chloride also with other additives, preferably participate in adjusting or improve flux composition some need the functional additive of character, combination.Such additive is as follows.
For example, flux composition of the present invention can also comprise at least one nonionic surface active agent or wetting agent, and when with other composition combinations, it can realize the surface tension of predetermined needs.Substantially, can use the nonionic surface active agent of any type, but preferred liquid is water miscible.Its example comprises the alcohol of ethoxylation, as nonyl phenol ethoxylate, alkylphenol is as Triton X-102 and Triton N101 (as from Union Carbide), the segmented copolymer of oxyethane and propylene oxide is as L-44 (from BASF AG (BASF)), with derived from Oleum Cocois, soybean oil, the tertiary amine ethoxylate (tertiary amine ethoxylate) (as the Ethomeen from Akzo Nobel N.V. (AKZO NOBEL)) of oleic acid or butter, alkylphenol, fatty alcohol, lipid acid, in molecule, contain the aliphatic amine of at least 12 carbon atoms or the polyethoxylated of acid amides and poly-propoxylated derivative, alkylaromatic hydrocarbon (alkylarene) sulfonate and dialkyl sulfosuccinates are as fatty alcohol and alicyclic alcohol, the polyglycol ether derivative of saturated and unsaturated fatty acids and alkylphenol, described derivative preferably contains 3-10 ethylene glycol ether group and 8-20 carbon atom and contains 6-18 carbon atom at the moieties of alkylphenol in (aliphatic series) hydrocarbon part, the water-soluble adducts of polyethylene oxide and polypropylene glycol, on alkyl chain, contain the quadrol polypropylene glycol (ethylene-diaminopolypropylene glycol) of 1-10 carbon atom, its with contain 20-250 ethylene glycol ether group and/or 10-100 propylene glycol group additivity, and composition thereof.The common each propylene glycol of such compound unit contains 1-5 ethylene glycol (EO) unit.Representational example is nonylphenol-polyethoxyethanols, Viscotrol C polyglycol ether, poly(propylene oxide)-polyethylene oxide adducts, tributyl-phenoxy group polyethoxye-ethanol, polyoxyethylene glycol and phenoxy group polyethoxyethanols.Fatty acid ester (as polyethylene Span 85), glycerine, Sorbitan, sucrose and tetramethylolmethane of polyethylene sorbitanic and composition thereof is also suitable nonionic surface active agent.Low-foam wetting agents, as U.S. Patent number 7,560, the tertiary mixture of describing in 494 is also suitable.The nonionic surface active agent of commercially available the above-mentioned type comprises with the trade(brand)name of OXETAL, ZUSOLAT and PROPETAL to be sold by Zschimmer and Schwarz company limited (Zschimmer & Schwarz GmbH & Co KG) (German Lai Ensitan), the tensio-active agent of being sold by Alfa Kimya company (Turkey, istanbul) with trade(brand)name with NETZER SB II.The suitable nonionic surface active agent of various ranks is sold with trade(brand)name MERPOL.
The hydrophilic-lipophilic balance value (HLB) of at least one described nonionic surface active agent is not an important parameter of the present invention and can be by those skilled in the art in the wide region of 3-18, for example, in the scope of 6-16, selects.For example, the HLB of MERPOL-A is 6-7, and the HLB of MERPOL-SE is 11, and the HLB of MERPOL-HCS is 15.Another feature of nonionic surface active agent is that its cloud point (is the confirmable temperature being separated, for example, by ASTM D2024-09 standard method of test; This phenomenon is the feature of the nonionic surface active agent that contains polyoxyethylene chain, and it shows the solubleness contrary with temperature and therefore " occurs muddy (cloud-out) " rising under certain temperature in water; Confirmation has the glycol of this phenomenon to be called as " cloud point glycols "), it can be preferably higher than melting the flux working temperature of bathing (fluxing bath) as undefined with respect to using in hot dip galvanizing method.Preferably the cloud point of nonionic surface active agent should be higher than 90 ℃.
The suitable amount of nonionic surface active agent is well known to those skilled in the art and conventionally accounting in the scope of flux mixture 0.02-2.0 % by weight, and preferably 0.5-1.0 % by weight depends on the type of compounds of selection.
Flux composition of the present invention can also comprise at least one corrosion inhibitor, especially under oxidisability or acidic conditions, suppresses the compound of the oxidation of steel.In one embodiment, corrosion inhibitor comprises at least one amino.Comprise the speed of iron accumulation during this aminoderivative corrosion inhibitor can significantly be reduced in flux tank at flux composition." aminoderivative corrosion inhibitor " refers to herein and suppresses the oxidation of steel and contain amino compound.Fat alkylamine and quaternary ammonium salt (preferably containing 4 independently alkyl groups of the selection of 1-12 carbon atom), if nitric acid alkyl dimethyl quaternary ammonium (alkyl dimethyl quaternary ammonium nitrate) is the suitable example of this type of aminocompound.Other suitable examples comprise hexanediamine.In another embodiment, corrosion inhibitor comprises at least one hydroxyl, or comprises hydroxyl with amino simultaneously and known by those skilled in the art.The suitable amount of corrosion inhibitor is well known to those skilled in the art and conventionally in the scope of 0.02-2.0 % by weight, and preferably 0.1-1.5 % by weight or 0.2-1.0 % by weight depends on the type of compounds of selection.Flux composition of the present invention can comprise at least one corrosion inhibitor and nonionic surface active agent or wetting agent as defined above simultaneously.
In any above-mentioned embodiment, flux composition of the present invention is not preferably containing volatile organic matter, and for example acetic acid, boric acid and methyl alcohol, especially law are forbidden the organism (security, toxicity) for zinc-plated unit.
Flux composition of the present invention can be produced by multiple methods.They can be by the order with possible arbitrarily in one or more mixing steps, by basal component (be zinc chloride, ammonium chloride, basic metal and/alkaline earth metal halide, lead chloride and tin chloride) and, if necessary, optional composition (being alkyl quaternary ammonium salts, other transition metal or rare-earth metal chloride, corrosion inhibitor and/or nonionic surface active agent) mixes, and preferably thoroughly mixes (for example, under high-shear) and produces simply.Flux mixture of the present invention also can pass through the production in series of at least two steps, one of them step is included in ammonium chloride or sodium-chlor or its mixture dissolves lead chloride, and in a rear step, the solution of the lead chloride in ammonium chloride or sodium-chlor or its mixture then with other basal components (being zinc chloride, Repone K, tin chloride) and, if necessary, the optional member in composition (as above-mentioned listed) mixes.In an embodiment of a rear method, in the situation that existing, water carries out the dissolving of lead chloride.In another embodiment of a rear method, can in aqueous mixture, dissolve the amount of the lead chloride of 8-35g/l, described aqueous mixture comprises ammonium chloride and/or sodium-chlor and the remaining water of 150-450g/l.Particularly, dissolving step below can be implemented the time of 4-30 minute in the temperature range of 55 ℃-75 ℃, and preferably with stirring.
A significant advantage of flux composition of the present invention is that it applies (use) field widely.Flux composition of the present invention is specially adapted to use the zinc alloy of wide region and the hot dip galvanizing method in batches of pure zinc.In addition, the continuous zinc coating method that flux of the present invention also can be used for using zinc-aluminium or zinc-aluminium-magnesium or pure zinc to bathe, for zinc-plated wide tinsel (as metal wire, pipeline, pipe, volume, plate) on a large scale especially from iron material as iron and steel (as band steel and long product made from steel).
According to a further aspect, therefore the present invention relates to zinc-plated, and particularly the melting of galvanizing is bathed, wherein in the water-soluble or aqueous medium according to the flux composition of any in above-mentioned embodiment of suitable amount.Make based on zinc chloride, ammonium chloride, basic metal or alkaline earth metal chloride and one or more transition metal chlorides (for example plumbous, tin) and optionally the water-soluble method of flux composition of other metal chlorides (nickel, cobalt, cerium, lanthanum) be well known.Within the total concn of component that melts the flux composition in bathing can the scope restriction at non-constant width, as 200-750g/l, preferably 350-750g/l, most preferably 500-750g/l or 600-750g/l.In operating in batches or continuously, the hot dip galvanizing method that is particularly useful for using the bath of zinc-aluminium is bathed in this melting, but is also applicable to the zinc-plated bath of pure zinc.
The melting using in method of the present invention (in batches or continuously) is bathed preferably remain on 50 ℃-90 ℃, and preferably 60 ℃-90 ℃, most preferably in the temperature range of 65 ℃-85 ℃.This method comprise in the above-described embodiment any flux bathe in, process (melting), the step of for example soaking metal products.Preferably, in interruption (in batches) operation, described treatment step carries out with the productive rate speed in the scope of 1-12m/ minute or 2-8m/ minute, maintain 0.01-30 minute, or 0.03-20 minute, or 0.5-15 minute, or the time of 1-10 minute scope, depend on following operating parameters, the composition that for example melting is bathed and/or temperature, the composition that needs zinc-plated metal (for example steel), shape and/or the size of goods.As those skilled in the art know, may there be large difference in the treatment time of goods with the treatment time of another goods.Shorter time (approach or even lower than 0.1 minute) is applicable to metal wire, and the longer time (approaching 15 minutes or more) is more suitable for, for example bar.In operate continuously, metal treatment step, in being immersed in and melting and bathe, can 0.5-10m/ minute, or the speed of 1-5m/ minute is carried out.Also can reach more speed, 10-100m/ minute, as 20-60m/ minute.
In fact, can process in this way the metallic surface that is easy to arbitrarily corrosion, the iron of for example any type or steel work.Shape (whether flat), geometrical shape (whether complexity) or the size of metal products are not important parameters of the present invention.Need zinc-plated goods can be called as long products.To refer to that at least 10 times of the dimensions (length) of product are greater than two other other dimension (relative with flat product for term " long products " herein, at least 10 times of two dimensions (length and width) are greater than thickness, i.e. the 3rd dimension) as, whether curling metal wire is (, be used for production example as bolt and fence), bar, bobbin, strengthen rod, pipe (welding or seamless), guide rail, structural shape and part (for example I-shaped steel, H-shaped steel, L-shaped steel, T-shaped steel etc.), or the pipeline of any dimension, for example, for civil construction, mechanical engineering, the energy, transportation (railway, electric car), family expenses and furniture.Need zinc-plated metal products can be also, be not limited to the form with flat product, as flat board, plate, panel, from slab, (50-250mm is thick, 0.6-2.6m is wide, and at most 12m are long) the hot rolling bar of rolling and cold rolling (width 600mm and more than, or lower than 600mm, provide with routine coiling coil or overlapping layer) and can be used for automobile, heavy-duty machinery, building, packing and electrical equipment.
In any galvanized method, be important on the surface of implementing to melt before step the zinc-plated goods of cleaning requirement suitably.Realizing the technology of the surface cleaning of desirability and know for those skilled in the art, and can repeat, clean as alkalescence, is then that water rinses, with pickling and last water flushing.Although these all programs are known, explanation is below to exist for complete object.
Can carry out easily alkali cleaning as the water-based alkaline compositions of washing assistant and kinds of surface promoting agent with also containing phosphoric acid salt and silicate.The free basicity (free alkalinity) of this aqueous detergent can be very different.Therefore,, in initial manufacture step, metal products passes through at de-grease bath as the cleaning (de-oiling fat) in ultrasonic wave, the de-grease bath of alkalescence.Then,, in second step, rinse the metal products through de-oiling fat.Next step, the one or more following cleanup acid treatment of metal products process: at the temperature of 15 ℃-60 ℃, within the time of 1-90 minute (preferably 3-60 minute), pass through in water-based strong acid media, for example hydrochloric acid or sulfuric acid, and the optionally immersion in the situation that of iron protochloride and/or iron(ic) chloride existence.Conventionally use acid concentration for about 5-15 % by weight, as 8-12 % by weight, but also can use denseer acid.In continuation method, pickling time conventionally in the 5-30 scope of second, is more typically in 10-15 second.In order to prevent over-pickling, in bathing, pickling can comprise at least one corrosion inhibitor, normally cats product or amphoterics, is generally 0.02-0.2 % by weight, preferably the amount of 0.05-0.1 % by weight.Can simply immerse pickling tank by goods and complete pickling.Also can use other procedure of processing.For example, energy machinery or ultrasonic agitation goods, and/or electric current can flow through goods for electricity-pickling.As everyone knows, these extra technology modes significantly shorten the time of pickling conventionally.Significantly, if needed, these pre-treatment step can separately or be cycled to repeat until reach the clean-up performance needing.Then, preferably after cleaning, process immediately (melting) metal products, for example, in melting of the present invention is bathed, preferably under above-mentioned total salt concentration, temperature and time condition, soak, thereby form protective membrane on its surface.
Metal (as iron or the steel) goods that melt, after soaking in melting is bathed within the suitable time and at suitable temperature, are preferably dried subsequently.According to the condition of prior art, the dry metal products that can melt by transfer is through having air atmosphere, the process furnace of for example forced air flow tells on, wherein heating of metal goods at the temperature of 220 ℃-250 ℃, until its surface shows the temperature between 170 ℃ and 200 ℃, for example, maintain 5-10 minute.But, also surprisingly find that the heating condition of milder is more applicable in the time using flux composition of the present invention or its any embodiment.
Therefore it may be enough that the surface that, has been found that metal in drying step (as steel) goods shows the temperature of 100 °-200 ℃.This can also can realize by the atmosphere that uses weak oxide in drying step by for example using the Heating temperature of 100 ℃-200 ℃ to realize this.In an embodiment of the invention, the surface temperature of metal products can be from 100 ℃-160 ℃, or 125-150 ℃, or 140-170 ℃.In another embodiment, dry can be at 0.5-10 minute, or tell in the time of 1-5 minute.In another embodiment, dry can telling in specific gas atmosphere, as the air atmosphere that dewaters, nitrogen atmosphere or except Shuifu County's nitrogen air atmosphere (if nitrogen gas concn is wherein more than 20%) dewaters.
In the next step of galvanized method, melting and dry metal products are dipped in the zinc-plated bath of molten zinc-based, to form metallic coating on goods.As everyone knows, the immersion time can depend on that one group of parameter limits, comprise the size and dimension (as flat or long) of goods, the coat-thickness of needs and definite composition, particularly aluminium content (in the time using Zn-Al alloy as zinc-plated bath) or the Mg content (in the time using Zn-Al-Mg alloy as zinc-plated bath) that zinc is bathed.In one embodiment, the zinc-plated bath of molten zinc-based can comprise (a) 4-24 % by weight (as 5-20 % by weight) aluminium, (b) 0.5-6 % by weight (as 1-4 % by weight) magnesium, and (c) all the other are zinc substantially.In another embodiment, the zinc-plated bath of molten zinc-based can comprise other elements of trace (1.0 % by weight are following) or trace (being inevitable impurity), such as but not limited to, silicon (as many as 0.3 % by weight), tin, lead, titanium or vanadium.In another embodiment, can in this treatment step of a part, stir the zinc-plated bath of molten zinc-based.In this step, the zinc-plated bath of zinc-base preferably remains in the temperature range of 360 ℃-600 ℃.Surprisingly find that the temperature that uses flux composition of the present invention can reduce immersion step obtains the thin protective coating of high-quality simultaneously; can within the time extending, keep its protectiveness effect; as 5 years or more; or even 10 years or more, this depends on the type (atmospheric moisture, temperature etc.) of envrionment conditions.Therefore, in an embodiment of the invention, zinc-plated molten zinc-based bath is remained on to 350 ℃-550 ℃, or 380-520 ℃, or in the temperature range of 420-520 ℃, optimum temps depends on the aluminium that optionally exists in the bath based on zinc and/or the content of magnesium.In another embodiment of galvanized method of the present invention, at the temperature between 380 ℃ and 440 ℃, implement to immerse, and the zinc-plated bath of described molten zinc-based comprises (a) 4-7 % by weight aluminium, (b) 0.5-3 % by weight magnesium, and (c) all the other are zinc substantially.
In an embodiment of the invention, can be 5-50 μ m, for example 8-30 μ m by the thickness at the protective coating obtaining by the upper enforcement immersion of the pretreated metal products of flux composition of the present invention (as ferrous products or steel work) step.This can be selected suitably by those skilled in the art; depend on series of parameters, comprise that the thickness of metal products and/or shape, metal products estimate the expectation weather resistance in the time of the protective coating of the pressure of tolerance and envrionment conditions, formation etc. in its life-span.The coating that for example 5-15 μ m is thick is suitable for the steel work thick lower than 1.5mm, and the thick coating of 20-35 μ m is suitable for exceeding the steel work that 6mm is thick.
Finally, metal (as iron or steel) goods remove and are cooling from zinc-plated bath.This cooling step can be immersed in the water or make simply its cooling enforcement easily in air by zinc-plated metal products.
Have been found that hot dip galvanizing method of the present invention allows on iron or steel work (flat product and long products) continuously or in batches deposition thinner, more evenly, more smoothly and not containing the protective coating in hole, when the zinc-aluminium that especially contains the zinc that is no more than 95% when use or the zinc-plated bath of zinc-aluminium-magnesium.For roughness, the quality of coatingsurface is equal to or better than the quality reaching according to the conventional H DG zinc layer of EN ISO1461 (using other metals that are no more than 2% in zinc is bathed).For erosion resistance, coating of the present invention reaches approximately 1000 hours, its approximately 600 hours of reaching far above the conventional H DG zinc layer according to EN ISO1461 in the salt spray test of ISO9227.In addition, also can use in the present invention the zinc-plated bath of pure zinc.
In addition, method of the present invention is well suited in the steel work to arbitrary shape (flat, cylindrical etc.), as metal wire, plate, pipe, bar, reinforcing bar etc. carry out zinc-plated, described goods are made up of various steels, particularly, described goods are made up of the steel grade and the stainless steel that contain carbon content and be up to 0.30 % by weight, phosphorus content 0.005-0.1 % by weight and silicone content 0.0005-0.5 % by weight.The classification of steel grade is well known to those skilled in the art, specifically by Society of automotive engineers (SAE).In one embodiment, metal can be chromium/nickel steel or the chromium/nickel/molybdenum steel that is easy to corrosion.Optionally, steel grade can contain other elements as sulphur, aluminium and copper.Suitable example includes but not limited to, be known as AISI304 (* 1.4301), AISI304L (1.4307,1.4306), the steel grade of AISI316 (1.4401), AISI316L (1.4404,1.4435), AISI316Ti (1.4571) or AISI904L (1.4539) [* 1.xxxx=is according to DIN10027-2].In other embodiments of the present invention, metal can be the steel grade that is called S235JR (according to EN10025) or S460MC (according to EN10149) or 20MnB4 (* 1.5525, according to EN10263).
Provide the following examples to understand and to show the present invention, and should not form limitation of the scope of the invention, scope of the present invention is only defined by the appended claims.
embodiment 1-zinc-plated general step at 440 ℃
The steel plate (2mm is thick, and 100mm is wide and 150mm long) of being manufactured by steel grade S235JR (weight content: 0.114% carbon, 0.025% silicon, 0.394% manganese, 0.012% phosphorus, 0.016% sulphur, 0.037% chromium, 0.045% nickel, 0.004% molybdenum, 0.041% aluminium and 0.040% bronze medal) according to the pre-treatment of step successively below:
-at 65 ℃, carry out the alkaline de-oiling fat for the first time of 20 minutes by the mode of SOLVOPOL SOP (50g/l) and surfactant mixture EMULGATOR SEP (10g/l), both purchased from Lutter Galvanotechnik company;
-water rinses;
-at 25 ℃, at (the composition: 10 % by weight HCl, 12 % by weight FeCl of the bath based on hydrochloric acid
2) in pickling for the first time 1 hour;
-water rinses;
-in the de-grease bath that uses the composition identical with first above-mentioned step, carry out the alkaline de-oiling fat for the second time of 10 minutes;
-water rinses;
-pickling for the second time 10 minutes in pickling with above-mentioned identical composition is bathed;
-water rinses,
-in the case of 0.3%Netzer4 (purchased from the non-ionic type wetting agent of Lutter Galvanotechnik company) exists, as below form described in the concentration flux composition that is 650g/l in melt steel plate 180 seconds;
-at 100-150 ℃, be dried 200 seconds;
-at 440 ℃, take the immersion speed of 1.4m/ minute the steel plate of the silicon that contains 5.0 % by weight aluminium, 1.0 % by weight magnesium, trace and lead, all the other zinc-plated meltings in the bath based on zinc of zinc 3 minutes; And
-cooling through zinc-plated steel plate in air.
embodiment 2-18-used exemplary flux composition of the present invention before 440 ℃ zinc-plated
steel processing
The experimental procedure that has repeated embodiment 1 with multiple flux composition, wherein the ratio of multiple muriate component is as listed in table 1.The quality of estimating to evaluate with the per-cent (being expressed as the standard of 0-100) on the perfect steel surface applying of alloy coating by three people's team, this numerical value representing in last hurdle of table 1 is the mean value of these three separate marking.In the time keeping melting to bathe at 72 ℃ (embodiment 1-12 is not with asterisk) or 80 ℃ (embodiment 13-18, asterisk mark), evaluate coating quality.
table 1
table 1 (end)
The flux composition of embodiment 1,3 and 5 also contains the NiCl of 1 % by weight
2reach 100 % by weight to meet.
comparative example 19-22
The experimental procedure that has repeated embodiment 1 with the multiple flux composition according to prior art, wherein the ratio of multiple muriate component is as listed in table 2.By the coating quality of method evaluation identical in embodiment before.
table 2
The flux composition of embodiment 19 contains 1 % by weight NiCl extraly
2reach 100 % by weight to meet.
These comparative examples prove when flux composition is not when chloride containing tin or lead chloride, or the total amount of tin chloride and lead chloride is below 2.5 % by weight time, if the coating quality of evaluating in embodiment 2-18 is non-constant.
embodiment 23-zinc-plated general step at 520 ℃
Repeat the step successively of embodiment 1, use the treatment step of flux composition to implement at 80 ℃, difference is, in penultimate step zinc-plated at 520 ℃ with the immersion speed of 4m/ minute, in the silicon that contains 20.0 % by weight aluminium, 1.0 % by weight magnesium, trace and lead, the bath based on zinc that all the other are zinc, carry out.
embodiment 24-31-used illustrative flux composition of the present invention before 520 ℃ zinc-plated
steel processing
Repeated the experimental procedure of embodiment 23 with multiple flux composition, wherein the ratio of multiple muriate component lists as table 3 below.As evaluated coating quality in embodiment 2-18.
table 3
(table 3 finishes)
the zinc-plated general step of steel plate of embodiment 32-sclerosis
Process according to the following steps the thick steel plate of 1.2mm of being made by the steel grade 22MnB5 hardening (weight content: 0.257% carbon, 0.27% silicon, 1.32% manganese, 0.013% phosphorus, 0.005% sulphur, 0.142% chromium, 0.018% nickel, 0.004% molybdenum, 0.031% aluminium, 0.009% bronze medal and 0.004% boron):
-use grit sandblast 8 minutes;
-in the commercially available sanitising agent (solution 10 % by weight and 2g/l inhibitor Rodine A31) of the trade(brand)name Novaclean N purchased from Henkel Corp. (Henkel), clean 30 minutes;
-water rinses;
-as mentioned above, at 80 ℃, and be called at the commodity purchased from Lutter Galvanotechnik company of 3ml/l Netzer4 (from the non-ionic type wetting agent of Lutter Galvanotechnik company) and 10ml/l under the corrosion inhibitor existence of PM, the steel plate that melts sclerosis in the flux composition that is 650g/l in concentration, continues 180 seconds.Particularly, flux composition contains 59 % by weight zinc chloride, 20 % by weight ammonium chlorides, 3 % by weight sodium-chlor, 12 % by weight Repone K, 4 % by weight tin chlorides, 1 % by weight lead chloride and 1 % by weight nickelous chloride;
-at 100-150 ℃, be dried 120 seconds;
-at 440 ℃ with the immersion speed of 1.4m/ minute, comprising 5.0 % by weight aluminium and 1.0 % by weight magnesium, all the other are in the bath based on zinc of zinc, or at 520 ℃, comprising 20.0 % by weight aluminium and 2.0 % by weight magnesium, all the other are in the bath based on zinc of zinc, the steel plate of the zinc-plated sclerosis through melting 3 minutes; And
-cooling through zinc-plated hardened steel plate in air.
the general step that embodiment 33-steel wire is zinc-plated
Process according to the following steps the metal wire (diameter 4.0mm) of being made by steel grade 22MnB5 (content: 0.056% carbon, 0.179% silicon, 0.572% manganese, 0.011% phosphorus, 0.022% sulphur, 0.097% chromium, 0.074% nickel, 0.009% molybdenum, 0.004% aluminium and 0.187% bronze medal):
-at 60 ℃, carry out primary 10 seconds alkaline de-oiling fat by the mode of SOLVOPOL SOP (50g/l) and surfactant mixture Emulgator Staal (10g/l), both purchased from Lutter Galvanotechnik company;
-water rinses 2 seconds;
-at 50 ℃, (form: 12 % by weight HCl, 10 % by weight FeCl in the bath based on hydrochloric acid
2, 1 % by weight FeCl
3, 10ml/l is purchased from Emulgator DX and the 10ml/l inhibitor PM of Lutter Galvanotechnik company) in pickling 10 seconds;
-water rinses 2 seconds;
-at 82 ℃, and in the case of 3ml/l Netzer4 (purchased from the wetting agent of Lutter Galvanotechnik company) exists, at flux composition as herein described (particularly, flux composition comprises 59 % by weight zinc chloride, 20 % by weight ammonium chlorides, 3 % by weight sodium-chlor, 12 % by weight Repone K, 4 % by weight tin chlorides, 1 % by weight lead chloride and 1 % by weight nickelous chloride) the middle steel wire that melts, continue 2 seconds;
-dry until the surface temperature of metal wire reaches 100 ℃;
-at 440 ℃, comprising the silicon of 5.0 % by weight aluminium, 1.0 % by weight magnesium, trace and lead, the bath based on zinc that all the other are zinc, or at 520 ℃, comprising in 20.0 % by weight aluminium and 2.0 % by weight magnesium, 0.12 % by weight silicon, the bath based on zinc that all the other are zinc, the zinc-plated steel wire through melting, continues 6 seconds; And
-cooling through zinc-plated steel wire in air.
embodiment 34-is steel plate galvanized at 510 ℃
Process according to the following steps the steel plate (thickness 2.0mm) of being made by steel grade S235JR (as forming of definition in embodiment 1):
-at 60 ℃, carry out the alkaline de-oiling fat for the first time of 30 minutes by the mode of SOLVOPOL SOP (50g/l) and surfactant mixture Emulgator Staal (10g/l), both purchased from Lutter Galvanotechnik company;
-water rinses;
-at 25 ℃, (form: 12 % by weight HCl, 15 % by weight FeCl in the bath based on hydrochloric acid
2, 1 % by weight FeCl
3, purchased from 2ml/l inhibitor HM and the 2.5ml/lEmulgator C75 of Lutter Galvanotechnik company) in carry out pickling for the first time, continue 60 minutes;
-water rinses;
-at 60 ℃, pass through mode alkaline grease bath 5 minutes that take off for the second time of SOLVOPOL SOP (50g/l) and surfactant mixture Emulgator Staal (10g/l), both purchased from Lutter Galvanotechnik company;
-water rinses;
-at 25 ℃ with the bath based on hydrochloric acid of acid pickling step same composition for the first time in carry out pickling for the second time, continue 5 minutes;
-water rinses;
-at 80 ℃ in the flux composition (comprising 60 % by weight zinc chloride, 20 % by weight ammonium chlorides, 3 % by weight sodium-chlor, 12 % by weight Repone K, 4 % by weight tin chlorides and 1 % by weight lead chloride) of total salt concentration 750g/l and in the case of 1ml/l Netzer4 (purchased from the wetting agent of Lutter Galvanotechnik company) exist, by using 4n/ minute or higher draw speed melting steel plate, continue 3 minutes;
-dry until the surface temperature of steel plate reaches 120 ℃;
-at 510 ℃, comprising lead, all the other steel plates for zinc-plated melting in the bath based on zinc of zinc of 20.0 % by weight aluminium, 4.0 % by weight magnesium, 0.2 % by weight silicon, trace, continue 3 minutes; And
-cooling zinc-plated steel plate in air.
This step is found the excellent coating quality that provides similar to embodiment 24.The following variant of this step also provides excellent coating quality:
The same, difference is 650g/l total salt concentration, in flux 2ml/l Netzer4 and zinc-plated in the bath based on zinc at 490 ℃,
The same, difference is 650g/l total salt concentration, in flux 2ml/l Netzer4 and at 500 ℃ in the bath based on zinc zinc-plated 1 minute,
The same, difference is 650g/l total salt concentration, in flux, melt 5 minutes under 2ml/l Netzer4 and at 510 ℃ in the bath based on zinc zinc-plated 10 minutes,
The same, difference is 650g/l total salt concentration, in flux, melt 5 minutes under 2ml/l Netzer4 and at 530 ℃ in the bath based on zinc zinc-plated 5 minutes, and
The same, difference is 650g/l total salt concentration, in flux, melt 5 minutes under 2ml/l Netzer4 and at 530 ℃ in the bath based on zinc zinc-plated 15 minutes.
embodiment 35-is steel plate galvanized at 520 ℃
According to the steel plate (thickness 2.0mm) of being made by steel grade S235JR (as the composition of definition in embodiment 1) with step process identical in embodiment 34, the operational condition except following:
-melting in step, total salt concentration 650g/l in the situation that 2ml/l Netzer4 exists, and
-at 520 ℃, comprising 20.0 % by weight aluminium, 2.0 % by weight magnesium, 0.13 % by weight silicon, trace lead, all the other are the zinc-plated step of 3 minutes in the bath based on zinc of zinc.
This step is found the excellent coating quality that provides similar to embodiment 24.
Claims (10)
1. the flux composition for the treatment of metallic surface, described composition comprises that (a) exceedes the zinc chloride of 40 % by weight lower than 70 % by weight, (b) ammonium chloride of 10-30 % by weight, (c) exceed one group at least two kind alkali metal halides or the alkaline earth metal halide of 6 % by weight lower than 30 % by weight, (d) 0.1-2 % by weight lead chloride, and (e) 2-15 % by weight tin chloride, prerequisite is that the combined amount of lead chloride and tin chloride accounts for described composition at least 2.5 % by weight.
2. flux composition as claimed in claim 1, it is characterized in that, described one group of at least two kinds of alkali metal halide or alkaline earth metal halide account for flux composition 10-30 % by weight and are that one group of at least two kinds of alkali metal chloride comprises sodium-chlor and the Repone K with KCl/NaCl weight ratio 0.2-8.0.
3. flux composition as claimed in claim 1 or 2, described composition also comprises at least one nonionic surface active agent and/or at least one corrosion inhibitor.
4. one kind melts bath, and it comprises the water-soluble flux composition as described in any one in claim 1-3, it is characterized in that, in water, the total concn scope of flux composition component is 200-750g/l.
5. for the zinc-plated method of metal products, the method is included in the temperature range of 50 ℃-90 ℃, in melting claimed in claim 4 is bathed, processes the step of described goods 0.01-30 minute.
6. galvanized method as claimed in claim 5, is characterized in that, described metal products is ferrous products or steel work.
7. the galvanized method as described in claim 5 or 6, is characterized in that, treated goods are further dried until its surface temperature reaches the scope of 100 ℃-200 ℃.
8. the galvanized method as described in any one in claim 5-7, described method also comprises in the zinc-plated bath based on zinc of treated goods immersion melting, described zinc-plated bath comprises the aluminium of (a) 4-24 % by weight, (b) magnesium of 0.5-6 % by weight, and (c) all the other are zinc substantially.
9. galvanized method as claimed in claim 8, it is characterized in that, at the temperature between 380 ℃ and 440 ℃, implement to immerse, and the zinc-plated bath based on zinc of described melting comprises the aluminium of (a) 4-7 % by weight, (b) magnesium of 0.5-3 % by weight, and (c) all the other are zinc substantially.
10. with the pretreated zinc-plated iron product of the flux composition as described in any one in claim 1-3 or a product made from steel, described product has the protective coating of thickness 5-30 μ m.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1219213.4A GB2507311B (en) | 2012-10-25 | 2012-10-25 | Flux compositions for steel galvanization |
| GB1219213.4 | 2012-10-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103774072A true CN103774072A (en) | 2014-05-07 |
| CN103774072B CN103774072B (en) | 2017-12-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310507727.4A Expired - Fee Related CN103774072B (en) | 2012-10-25 | 2013-10-24 | Flux composition for galvanizing steel |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US10793940B2 (en) |
| EP (1) | EP2725114B1 (en) |
| JP (1) | JP6113627B2 (en) |
| KR (1) | KR102014156B1 (en) |
| CN (1) | CN103774072B (en) |
| BR (1) | BR102013027374B1 (en) |
| CA (1) | CA2831050A1 (en) |
| DK (1) | DK2725114T3 (en) |
| ES (1) | ES2604409T3 (en) |
| GB (1) | GB2507311B (en) |
| HU (1) | HUE031072T2 (en) |
| PL (1) | PL2725114T3 (en) |
| PT (1) | PT2725114T (en) |
| RS (1) | RS55465B1 (en) |
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| CN110665778A (en) * | 2019-11-03 | 2020-01-10 | 江苏荣辉电力设备制造有限公司 | On-site repairing method for power transmission tower zinc coating |
| CN110724896A (en) * | 2019-11-03 | 2020-01-24 | 江苏荣辉电力设备制造有限公司 | Galvanizing method for scattered components of iron tower |
| CN112226751A (en) * | 2020-09-03 | 2021-01-15 | 余姚市永林机械科技有限公司 | Plating assistant liquid and hot galvanizing process using same |
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| GB2507309A (en) * | 2012-10-25 | 2014-04-30 | Fontaine Holdings Nv | Continuous single dip galvanisation process |
| PL2915607T3 (en) * | 2014-03-04 | 2019-11-29 | Fontaine Holdings Nv | Galvanized metal objects and their manufacturing process |
| CN105063530A (en) * | 2015-08-07 | 2015-11-18 | 昆山—邦泰汽车零部件制造有限公司 | Method for manufacturing high-hardness automobile hardware |
| CN105908113A (en) * | 2016-05-06 | 2016-08-31 | 长安大学 | Plating assistant agent for zinc-aluminum-nickel-rare earth-alloy hot-dip plating and technological method |
| WO2020118120A1 (en) | 2018-12-05 | 2020-06-11 | Surface Holdings Llc | Steel grit dryer |
| JP7311767B2 (en) * | 2019-08-30 | 2023-07-20 | 日本製鉄株式会社 | FLUX AND METHOD FOR MANUFACTURING Zn-Al-Mg-BASED PLATED STEEL PRODUCT USING THE SAME |
| IT201900018917A1 (en) * | 2019-10-15 | 2021-04-15 | Soprin S R L | SINGLE-DOSE CAPSULE FOR GALVANIZING BATHS |
| KR20230010323A (en) * | 2021-07-12 | 2023-01-19 | 전북대학교산학협력단 | Flux compositions for hot-dip galvanizing of zinc, aluminium and magnesium |
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Also Published As
| Publication number | Publication date |
|---|---|
| PL2725114T3 (en) | 2017-02-28 |
| CA2831050A1 (en) | 2014-04-25 |
| EP2725114B1 (en) | 2016-08-31 |
| KR102014156B1 (en) | 2019-08-26 |
| GB201219213D0 (en) | 2012-12-12 |
| RS55465B1 (en) | 2017-04-28 |
| CN103774072B (en) | 2017-12-12 |
| US20140120367A1 (en) | 2014-05-01 |
| DK2725114T3 (en) | 2016-12-19 |
| PT2725114T (en) | 2016-11-08 |
| GB2507311B (en) | 2018-08-29 |
| KR20150035342A (en) | 2015-04-06 |
| JP6113627B2 (en) | 2017-04-12 |
| JP2014088614A (en) | 2014-05-15 |
| HUE031072T2 (en) | 2017-06-28 |
| EP2725114A1 (en) | 2014-04-30 |
| US10793940B2 (en) | 2020-10-06 |
| GB2507311A (en) | 2014-04-30 |
| ES2604409T3 (en) | 2017-03-06 |
| BR102013027374A2 (en) | 2014-10-21 |
| BR102013027374B1 (en) | 2020-09-15 |
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